CN1854144A - Process for the production of silanol containing organopolysiloxanes - Google Patents
Process for the production of silanol containing organopolysiloxanes Download PDFInfo
- Publication number
- CN1854144A CN1854144A CNA2006100755187A CN200610075518A CN1854144A CN 1854144 A CN1854144 A CN 1854144A CN A2006100755187 A CNA2006100755187 A CN A2006100755187A CN 200610075518 A CN200610075518 A CN 200610075518A CN 1854144 A CN1854144 A CN 1854144A
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- China
- Prior art keywords
- equals
- general formula
- silicoorganic compound
- sub
- silanol group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000000034 method Methods 0.000 title claims abstract description 58
- 229920001296 polysiloxane Polymers 0.000 title description 22
- 238000004519 manufacturing process Methods 0.000 title description 4
- 230000008569 process Effects 0.000 title description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 title description 3
- 125000005372 silanol group Chemical group 0.000 claims abstract description 32
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 52
- 150000001875 compounds Chemical class 0.000 claims description 33
- 229910052763 palladium Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 14
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 3
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 150000003377 silicon compounds Chemical class 0.000 abstract 2
- 125000004429 atom Chemical group 0.000 abstract 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 abstract 1
- 229910010271 silicon carbide Inorganic materials 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 40
- -1 alkyl trichlorosilane Chemical compound 0.000 description 34
- 239000000203 mixture Substances 0.000 description 25
- 229910052739 hydrogen Inorganic materials 0.000 description 24
- 239000001257 hydrogen Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- HOPKHJSQWOIIQO-UHFFFAOYSA-N C[SiH2]C.[O] Chemical compound C[SiH2]C.[O] HOPKHJSQWOIIQO-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 238000005352 clarification Methods 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- UVTVLIRBQMMECM-UHFFFAOYSA-N [O].O[SiH](C)C Chemical compound [O].O[SiH](C)C UVTVLIRBQMMECM-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910020175 SiOH Inorganic materials 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NHOWDZOIZKMVAI-UHFFFAOYSA-N (2-chlorophenyl)(4-chlorophenyl)pyrimidin-5-ylmethanol Chemical compound C=1N=CN=CC=1C(C=1C(=CC=CC=1)Cl)(O)C1=CC=C(Cl)C=C1 NHOWDZOIZKMVAI-UHFFFAOYSA-N 0.000 description 1
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003619 algicide Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical class C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 229940031815 mycocide Drugs 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 229940094989 trimethylsilane Drugs 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a preparing method of organic silicon compound with silanol group and following general formula unit: H<SUB>a</SUB> (R'O) <SUB>b</SUB> (OH) <SUB>c</SUB>R<SUB>d</SUB>SiO<SUB> (4-a'-b-c-d)/2</SUB> (I), wherein a' is 0 or 1; b is 0 or 1; c is o or 1; d is 0, 1, 2 or 3; R can be the same or different, which represents 1-18 carbon atoms, silicon carbide valet and random selected replaced univalent hydrocarbyl group; R' can be the same or different, which represents interval of mixed atoms, random replaced univalent hydrocarbyl group with condition that the sum of a'+b+c+d not more than 3; a' and c is not 1 at the same time; each molecular of organic silicon compound of general formula (I) possesses at least one silicon bond OH group.
Description
Technical field
The present invention relates to have the manufacture method of the organopolysiloxane of silanol group, especially use the manufacture method of the functionalized straight chain organopolysiloxane of chain side silanol group.
Background technology
As everyone knows, under the simplest situation, the water-based hydrolytic action of the silicoorganic compound that silanol group can be by containing SiCl makes.And under the situation of monomeric silanes, it is relatively easy making specific silanol and it is separated into respective pure form with this method, but be used for the similar reaction of synthesized polymer silicoorganic compound, especially have the silicoorganic compound of chain side silanol functional effect, then obviously more difficult.Can make on the chain side by the functionalized polymkeric substance of silanol group from the mixture of forming by dialkyldichlorosilan,s and alkyl trichlorosilane and optional trialkylchlorosilane by cohydrolysis in principle.But these products are not the specific compound with homogeneous structural, but by having the random mixture that a small amount of chain side silanol group and the strong or weak hydrolysate of branch degree are formed.So, can not reach synthetic target in this way with organopolysiloxane of chain side silanol group.
The synthetic another kind that contains the organopolysiloxane of silanol group may be the acidity or the base catalysis hydrolytic action of SiH functionality siloxanes.Even but it be known to those skilled in the art that with this method and still can't make specific compound that this is because the process of this reaction there is no specificity with homogeneous structural.The balance of the dehydrogenative condensation effect of established silanol group and the SiH base that still exists, the main polymer chain of initial reactant and fracture and equally by the condensation of the silanol group of acid or base catalysis are actually as the formation of the silanol group of side reaction and expection and carry out simultaneously.Therefore the result makes the random mixture that the polymkeric substance of and part bridging strong or weak by branch degree is formed.
So traditional hydrolysis method is not suitable for optionally synthesizing on the chain side with the functionalized organopolysiloxane of silanol group.
Summary of the invention
The purpose of this invention is to provide the method with above-mentioned shortcoming, this method is optionally synthesized on the chain side with the functionalized organopolysiloxane of silanol group.Can realize this purpose by the present invention.
The present invention relates to make the method for the silicoorganic compound that have silanol group and form by following general formula unit
H
a＇(R＇O)
b(OH)
cR
dSiO
(4-a＇-b-c-d)/2 (I)，
Wherein
A ＇ equals 0 or 1, is preferably 0,
B equals 0 or 1, is preferably 0,
C equals 0 or 1,
D equals 0,1,2 or 3,
R can be identical or different, and representative has the univalence hydrocarbyl that is substituted 1 to 18 carbon atom, silicon-carbon bond, optional, and
R ＇ can be identical or different, and representative can by heteroatoms at interval, the optional univalence hydrocarbyl that is substituted, its condition is: a ＇+b+c+d's and≤3, a ＇ and c are not 1 simultaneously, and each molecule of silicoorganic compound of general formula (I) has at least one silicon bond OH base,
This method comprises: under the situation that the catalyzer (B) that is selected from periodic table of elements VIII subgroup metal and compound thereof and optional cocatalyst (K) exist, make to have the SiH base and reacted with water (C) by the silicoorganic compound (A) that following general formula unit is formed
H
a(R＇O)
bR
dSiO
(4-a-b-d)/2 (II)，
Wherein
A equals 0 or 1,
The definition of b, d, R and R ＇ is same as described above,
Its condition is: a+b+d and≤3
And a ＇+c's and equal a,
And each molecule of silicoorganic compound of general formula (II) has at least one silicon bond hydrogen atom.
The example of radicals R is: alkyl, as methyl, ethyl, n-propyl, sec.-propyl, 1-normal-butyl, 2-normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl; Hexyl is as n-hexyl; Heptyl is as n-heptyl; Octyl group, as n-octyl and iso-octyl, as 2,2, the 4-tri-methyl-amyl; Nonyl is as n-nonyl; Decyl is as positive decyl; Dodecyl is as dodecyl; Octadecyl is as the Octadecane base; Cycloalkyl is as cyclopentyl, cyclohexyl, suberyl and methylcyclohexyl; Aryl is as phenyl, naphthyl, anthryl and phenanthryl; Alkaryl, as adjacent-,-, p-methylphenyl, xylyl and ethylbenzene base; And aralkyl, as phenmethyl, α-and β-styroyl.
The example of the radicals R that is substituted is: haloalkyl, and as 3,3,3-trifluoro n-propyl, 2,2,2,2 ＇, 2 ＇, 2 ＇-hexafluoro sec.-propyl and seven fluorine sec.-propyls; And halogenated aryl, as adjacent-,-and rubigan.
Radicals R is preferably the univalence hydrocarbyl with 1 to 6 carbon atom, more preferably methyl and phenyl.
The example of radicals R ＇ is identical with the described example of radicals R.Radicals R ＇ be preferably optional by one or more ether oxygen atom separated from one another at interval, have the alkyl of 1 to 8 carbon atom, more preferably methyl, ethyl, propyl group, butyl and 2-ethoxyethyl group are preferably methyl, ethyl and propyl group especially.
As the silicoorganic compound with SiH base (A), the preferred use has following general formula person
Wherein
The integer that e equals 0 to 1000 is preferably 80 to 500 integer, 100 to 200 integer more preferably,
The integer that f equals 1 to 200 is preferably 1 to 60 integer, and more preferably 1 to 16 integer is preferably 1 to 6 integer especially,
R
1Represent hydrogen atom or R, and
The definition of R is same as described above.
The organopolysiloxane of the preferred general formula (III) that uses, the average viscosity under 25 ℃ is preferably 10 to 100,000 square millimeters/second, more preferably 25 to 10,000 square millimeters/second, is preferably 50 to 1000 square millimeters/second especially.
Used organopolysiloxane (A) is commercially available product, and method commonly used makes in the available silicon chemistry.
Metal or its compound of the periodic table of elements VIII subgroup that uses as composition (B) are preferably platinum metals or its compound, more preferably ruthenium, rhodium, iridium, palladium and platinum or its compound.
The method according to this invention, used catalyzer (B) can be solid, the aqueous solution or are dissolved in any organic solvent or are incorporated into form on the solid support material.Be preferably the catalyzer (B) that is incorporated on the solid support material.
According to prior art, the inorganic or organic polymer that all use for this purpose is as SiO at present
2, Al
2O
3, clay, gac or organic resin, all be suitable as solid support material in principle.Catalyst support material is preferably gac or Al
2O
3, wherein be preferably palladium/gac, palladium/Al as composition (B)
2O
3And ruthenium/gac, more preferably palladium/gac.
The amount of catalyst system therefor (B) depends on the quantity of contained SiH base in the organopolysiloxane (A).Calculating with metallic element, is benchmark with the gross weight of used organopolysiloxane (A), and the usage quantity of catalyzer (B) is preferably 10 to 10,000ppm, and more preferably 20 to 1000ppm, is preferably 50 especially to 500ppm.
Catalyst system therefor (B) is commercially available product, or can make according to method commonly used in the Organometallic Chemistry.
Preferably after reaction stops or when the method according to this invention stops, removing once more by filtering the catalyzer that will be adhered on the solid support material, and optionally utilize again in addition or reclaim.
The optional cocatalyst (K) that uses is proton compound, negative hydrogen ion compound or oxidable reductive compound in the method according to this invention.Suitably the example of cocatalyst (K) is: organic acid, as formic acid, acetic acid, oxalic acid, citric acid and xitix; And low-molecular-weight organosilicon hydride, as trimethyl silane, triethyl silicane and tetramethyl disiloxane.
Preferred cocatalyst (K) is: formic acid, acetic acid, oxalic acid, citric acid, xitix, triethyl silicane and tetramethyl disiloxane, wherein more preferably formic acid, oxalic acid, xitix, triethyl silicane and tetramethyl disiloxane are preferably formic acid, triethyl silicane and tetramethyl disiloxane especially.
The usage quantity of cocatalyst (K) depends on the amount of catalyst system therefor (B).Metallic element with the interior 100 moles of % of catalyst system therefor (B) is a benchmark, and the usage quantity of cocatalyst (K) is preferably 25 to 1000 moles of %, and more preferably 50 to 500 moles of % are preferably 100 to 250 moles of % especially.
In the method according to the invention, can use cocatalyst (K) with the companion.If use wherein R as organopolysiloxane (A)
1Definition general formula (III) compound identical with R, then preferably use cocatalyst (K) with the companion, this is because thus significantly shortened in the reaction times, when especially using the functionalized low compound of the SiH of general formula (III).
In the method according to the invention, can use arbitrarily that water wherein is preferably complete demineralised water, distilled water and purified water (Aqua purificata) as composition (C), more preferably demineralised water fully.
The usage quantity of composition (C) depends on the quantity of contained SiH base in the organopolysiloxane (A).With contained SiH base in the organopolysiloxane (A) is benchmark, and used composition (C) is preferably equimolar amount or excessive.
Contained per 100 moles of %SiH bases in the organopolysiloxane (A), the usage quantity of water is preferably 100 to 200 moles of %, and more preferably 100 to 150 moles of % especially are preferably 100 to 120 moles of %.
Made silicoorganic compound with silanol group are preferably has following general formula person
Wherein
R
2Represent R or OH base,
G equals 0 to 199, is preferably 0 to 59, and more preferably 0 to 5, especially be preferably 0,
H equals 1 to 200, is preferably 1 to 60, and more preferably 1 to 6,
Its condition is: g+h's and equal f, and
The definition of R, e and f is same as described above.
The average viscosity of organopolysiloxane under 25 ℃ of the general formula that preferably makes according to the present invention (IV) is preferably 10 to 100,000 square millimeters/second, more preferably 25 to 10,000 square millimeters/second, is preferably 50 to 1000 square millimeters/second especially.
In category of the present invention, general formula (III) and (IV) being interpreted as: each the described unit with coefficient e in the general formula (III) and e, g in f or the general formula (IV) and h all can be in this organopolysiloxane molecule distributes in mode arbitrarily, as blocked or random mode.
The method according to this invention, this is reflected at and is preferably-10 ℃ to+150 ℃, more preferably+10 ℃ to+100 ℃, be preferably especially+25 ℃ to+80 ℃ temperature range in enforcement.
Solvent (E) can be used or do not used to the method according to this invention, for example to implement the viscosity of homogenizing or reduction reaction mixture, wherein preferably under the situation that solvent exists.
If add solvent (E), then be preferably polar organic solvent, it can improve water and organopolysiloxane consistency mutually, but itself does not react with interior contained SiH base of these silicoorganic compound (A) and the interior contained SiOH base of reaction product (D).The example of appropriate solvent is: tetrahydrofuran (THF), two alkane, glycol dimethyl ether, more preferably tetrahydrofuran (THF) or two alkane.
If use solvent (E), the organopolysiloxane (A) that then per 100 weight parts are used, the usage quantity of solvent (E) is preferably 1 to 500 weight part, and more preferably 5 to 200 weight parts are preferably 10 to 100 weight parts especially.
Composition used according to the invention (A), (B) and optional (K) and optional (E) all can be a kind of composition, also can be at least two kinds of single mixture of ingredients.
In addition, can use in the method according to this invention not and directly to participate in reaction and reaction process not produced dysgenic other materials (H).
The example of these other materials (H) is: emulsifying agent, change catalyzer, sanitas mutually; Antimicrobial material is as sterilant, mycocide or algicide; Smell material, smell inhibitor or anti-odorant agent, defoamer, rheology modifier, dyestuff, pigment, redox-stable agent, fire retardant, bright protective agent and thermo-stabilizer.In the method according to this invention, preferably do not use other materials (H).
In addition, the method according to this invention can be used as uniform 1 phase reaction, heterogeneous reaction or implements in the dispersion such as microemulsion or huge emulsion.Preferably implement as uniform 1 phase reaction.
If this method implements as 2 phase reactions, this is not preferred, then for example by producing less than 500 microns median size guaranteeing mutual not miscible phase homogenizing as much as possible, and produces big internal-response surface.The intense mixing of each reacting phase can be implemented by means of all known mixing systems in the prior art in principle, as all types of agitators, high speed agitator, as trade mark Ultra-Turrax by name
Product or similar dissolver system, by means of ultrasonic probe or ultrasonic bath, or for example in tandem reaction sequence by means of mixing device static or that move.
If this method is implemented in dispersion, this is not preferred equally, then correspondingly need emulsifying agent or tensio-active agent, as nonionic, anionic property, cationic or amphoteric emulsifier, wherein this dispersion can any way method well known by persons skilled in the art make.
In the method according to this invention, used various compositions be in known manner method mix mutually and implement the reaction.
Herein, the composition used according to the present invention can mix in any order mutually, introduces in the reaction and/or implements and react.But in the reaction process of very exothermic, preferably with composition (C), optional for the form of the mixture of composition (E), by being metered in the mixture of forming by composition (A), (B), optional (K) and optional (E) and optional (H).
The method according to this invention is preferably at environment atmospheric pressure, and promptly about 900 to 1,100 hundred handkerchiefs are implemented down, but also can implement under higher and lower pressure.
The method according to this invention can batch-type, semi continuous or continous way fully, in suitable reactor assembly, implement, as batch-type reactor, cascade batch-type reactor, recirculation reactor, fluid hose, tubular reactor, microreactor, impeller pump and their arbitrary combination.
After reaction according to the present invention stopped, the reaction product of gained can be according in addition purifying and/or the separation of present known any procedure of processing.If need, after reaction, for example volatile component and the optional solvent that uses can be removed by optional distillment under reduced pressure, and the catalyzer that is combined on the solid support material can be removed by filtration.
In addition, after the method according to this invention, can implement other procedure of processings arbitrarily, utilize these steps to regulate the performance of the silicoorganic compound of prepared in accordance with the method for the present invention pointedly.In the case, these procedure of processings in principle can according to prior art in the manner known to persons skilled in the art method implemented.
The advantage of the method according to this invention is, enforcement and with low cost easily.
The special advantage of the method according to this invention is, quantitatively, selectivity is high and essentially no side reaction ground is implemented.So, with the productive rate height and the purity height of the functionalized silicoorganic compound of silanol group.
Another advantage of the method according to this invention is that used catalyzer (B) can almost completely be removed with simple methods by filtration, thereby the catalyzer of residual non-expectation not in the reaction product.In addition, the catalyzer through reclaiming can be purified, utilize and/or send back in the material circulation.So the method according to this invention environmental protection and economizing on resources muchly.
Another advantage of the method according to this invention is, and is of many uses and be suitable for reaching continuously batch type process equally.
In addition, another advantage of the method according to this invention is, can be used for the functional silicoorganic compound of many SiH, as organic polysiloxane and organopolysiloxane resins.
Embodiment
Except as otherwise noted, in following embodiment, all umbers and percentage number average are based on weight.In addition, all viscosity datas are benchmark with 20 ℃ temperature all.Except as otherwise noted, following embodiment is at environment atmospheric pressure, under promptly about 1,000 hundred handkerchiefs, and room temperature, under promptly about 20 ℃ temperature, or implements under the temperature that is reached during mixed reactant under room temperature under the situation of no extra heating or refrigerating unit.
Embodiment 1:
2 gram water and 100 grams are made up of trimethylsiloxy unit, dimethylsilane oxygen base unit and hydrogen methyl-silicane oxygen base unit, active hydrogen content be 0.085% and viscosity be that 95 square millimeters/second linear siloxanes is dissolved in 70 and restrains in the tetrahydrofuran (THF)s, and sneak into 0.25 the gram palladium/gac (Pd/C, the palladium of 10 weight %).Be heated to 70 ℃ and under this temperature, stirred 5 hours, wherein discharge hydrogen.In the perfect vacuum, under 80 ℃, remove all volatile components subsequently, catalyzer is separated by filtration by distillment.Making viscosity and be 130 square millimeters/second and silanol group content is the product of the achromaticity and clarification of 84.9 mmoles/100 grams.The analytical results of NMR spectrum shows, quantitatively formed the chain side silanol group that is binding on the siloxane main chain (29Si-NMR: δ approximate-56 to-58ppm).
Embodiment 2:
4.6 gram water and 400 grams are made up of trimethylsiloxy unit, dimethylsilane oxygen base unit and hydrogen methyl-silicane oxygen base unit, active hydrogen content be 0.051% and viscosity be that 250 square millimeters/second linear siloxanes is dissolved in 280 and restrains in the tetrahydrofuran (THF)s, and sneak into 1.04 the gram palladium/gacs (Pd/C, the palladium of 10 weight %) and 0.104 the gram triethyl silicane.At room temperature stir, reaction mixture slowly is warming up to about 30 ℃, and discharges hydrogen.After the reaction of this slight exotherm is stopped, continuing down to stir 1 hour at 30 ℃.Postheating continues reaction 4 hours to reflux temperature (being about 70 ℃) under this temperature.In the perfect vacuum, under 80 ℃, remove all volatile components subsequently, catalyzer is separated by filtration by distillment.Making viscosity and be 290 square millimeters/second and silanol group content is the product of the achromaticity and clarification of 50.9 mmoles/100 grams.The analytical results of NMR spectrum shows, has quantitatively formed the chain side silanol group that is binding on the siloxane main chain.
Embodiment 3:
13.4 gram water and 625 grams are made up of hydrogen dimethylamino base siloxy units, dimethylsilane oxygen base unit and hydrogen methyl-silicane oxygen base unit, active hydrogen content be 0.084% and viscosity be that 230 square millimeters/second linear siloxanes is dissolved in 560 and restrains in the tetrahydrofuran (THF)s, and sneak into 2.09 the gram palladium/gacs (Pd/C, the palladium of 10 weight %).At room temperature stir, reaction mixture slowly is warming up to about 30 ℃, and discharges hydrogen.After the reaction of this slight exotherm is stopped, continuing down to stir 1 hour at 30 ℃.Postheating continues reaction 2 hours to reflux temperature (being about 70 ℃) under this temperature.In the perfect vacuum, under 80 ℃, remove all volatile components subsequently, catalyzer is separated by filtration by distillment.Making viscosity and be 285 square millimeters/second and silanol group content is the product of the achromaticity and clarification of 84.1 mmoles/100 grams.The analytical results of NMR spectrum shows, has quantitatively formed the end of the chain and the chain side silanol group that are binding on the siloxane main chain.
Embodiment 4:
5.3 gram water and 250 grams are made up of hydrogen dimethylamino base siloxy units, dimethylsilane oxygen base unit and hydrogen methyl-silicane oxygen base unit, active hydrogen content be 0.084% and viscosity be that 230 square millimeters/second linear siloxanes is dissolved in 225 and restrains in the tetrahydrofuran (THF)s, and sneak into 0.85 gram palladium/gac (Pd/C, the palladium of 10 weight %) and 37 milligrams of formic acid.At room temperature stir, reaction mixture slowly is warming up to about 30 ℃, and discharges hydrogen.After the reaction of this slight exotherm is stopped, continuing down to stir 1 hour at 30 ℃.Postheating continues reaction 4 hours to reflux temperature (being about 70 ℃) under this temperature.In the perfect vacuum, under 80 ℃, remove all volatile components subsequently, catalyzer is separated by filtration by distillment.Making viscosity and be 294 square millimeters/second and silanol group content is the product of the achromaticity and clarification of 84.0 mmoles/100 grams.The analytical results of NMR spectrum shows, has quantitatively formed the end of the chain and the chain side silanol group that are binding on the siloxane main chain.
Comparative example 1:
The 725 gram water of packing in advance and are cooled to about 0 ℃, sneak into the mixture of being made up of 252.6 gram dimethyldichlorosilane(DMCS)s, 2.17 gram trimethylchlorosilanes and 2.99 gram METHYL TRICHLORO SILANE lentamente.Add after the end, be heated to 30 ℃, and under this temperature, stirred 1 hour.In the perfect vacuum, under 100 ℃, with siloxanes phase and aqueous phase separation, remove residual micro-moisture, dissolved HCl and volatile short chain hydrolysing component subsequently by distillment.Make viscosity and be 2850 square millimeters/second viscous oil.The NMR spectrum analysis result of reaction product shows, has formed the cross-linked polymer of being made up of trimethylsiloxy unit, dimethylsilane oxygen base unit, hydroxyl dimethylsilane oxygen base unit and methyl-silicane oxygen base unit.Only detect the expection hydroxymethyl siloxy units of trace.
Comparative example 2:
With 25 gram tetrahydrofuran (THF)s sneak into that 110 grams are made up of trimethylsiloxy unit, dimethylsilane oxygen base unit and hydrogen methyl-silicane oxygen base unit, active hydrogen content be 0.028% and viscosity be in 410 square millimeters/second the linear siloxanes, be cooled to 0 ℃, and under this temperature, sneak into 0.6 gram water and 0.121 gram concentration is 10% the KOH aqueous solution.Under this temperature, stirred 3 hours, and, and allowed it continue reaction 2 hours this mixture heating up to 60 ℃.Add 0.014 gram acetic acid (100%) subsequently, and in the perfect vacuum, under 100 ℃, remove volatile component by distillment.Make viscosity after the filtration and be 150 square millimeters/second the colourless product of clarification.The NMR spectrum analysis result of reaction product shows, has formed the partial cross-linked mixture of polymers of being made up of trimethylsiloxy unit, hydroxyl dimethylsilane oxygen base unit, dimethylsilane oxygen base unit, methyl-silicane oxygen base unit and (cyclotrisiloxane base) dimethylsilane oxygen base unit.Only observe the hydroxymethyl siloxy units that has formed a small amount of expection.
Comparative example 3:
With 25 gram tetrahydrofuran (THF)s sneak into that 110 grams are made up of trimethylsiloxy unit, dimethylsilane oxygen base unit and hydrogen methyl-silicane oxygen base unit, active hydrogen content be 0.028% and viscosity be in 410 square millimeters/second the linear siloxanes, be cooled to 0 ℃, and under this temperature, sneak into 0.6 gram water and 0.08 gram concentration is 10% the HCl aqueous solution.Under this temperature, stirred 3 hours, and, and continued reaction 2 hours this mixture heating up to 60 ℃.Add 0.044 gram triethylamine subsequently, and in the perfect vacuum, under 100 ℃, remove volatile component by distillment.Make viscosity after the filtration and be 186 square millimeters/second the colourless product of clarification.The NMR spectrum analysis result of reaction product shows, has formed the partial cross-linked mixture of polymers of being made up of trimethylsiloxy unit, hydroxyl dimethylsilane oxygen base unit, dimethylsilane oxygen base unit and methyl-silicane oxygen base unit.Only observe the hydroxymethyl siloxy units that has formed a small amount of expection.
Embodiment 5:
1.1 gram water and 100 grams are made up of trimethylsiloxy unit, dimethylsilane oxygen base unit and hydrogen methyl-silicane oxygen base unit, active hydrogen content be 0.051% and viscosity be that 245 square millimeters/second linear siloxanes is dissolved in 70 and restrains in the tetrahydrofuran (THF)s, and sneak into 0.26 the gram palladium/gac (Pd/C, the palladium of 10 weight %).In addition, be benchmark with the amount of palladium metal in the Pd/C, will be added in the reaction mixture according to the cocatalyst of listed equimolar amount in the table.At room temperature stir, this reaction mixture slowly is warming up to about 25 to 30 ℃, and discharges hydrogen.Postheating is to reflux temperature (being about 70 ℃), and continuation was reacted 2 hours under this temperature, is measured the reaction conversion ratio (referring to subordinate list) of SiH by the NMR spectrum.In the perfect vacuum, under 80 ℃, remove all volatile components subsequently by distillment, and by the filtering separation catalyzer.Make the product of achromaticity and clarification with the chain side silanol group that is binding on the siloxane main chain.
Table:
| 5a | 5b | 5c | 5d | 5e | 5f | |
| Cocatalyst | - | Formic acid | Acetic acid | Oxalic acid dihydrate | Triethyl silicane | 1,1,3, the 3-tetramethyl disiloxane |
| Amount (milligram) | - | 11.3 | 14.6 | 30.8 | 26.0 | 16.4 |
| Transformation efficiency after 1 hour/30 ℃ | 34％ | 87％ | 49％ | 72％ | 62％ | 83％ |
| Transformation efficiency after 1 hour/70 ℃ | 65％ | 100％ | 91％ | 100％ | 85％ | 100％ |
| Transformation efficiency after 2 hours/70 ℃ | 87％ | 100％ | 98％ | 100％ | 100％ | 100％ |
| Product viscosity [square millimeter/second] | 305 | 315 | 310 | 314 | 316 | 318 |
| SiOH content in the product [mmole/100 grams] | 44.3 | 51.1 | 51.0 | 50.8 | 51.0 | 50.9 |
Embodiment 6:
1.7 gram water and 100 grams are made up of trimethylsiloxy unit, dimethylsilane oxygen base unit and hydrogen methyl-silicane oxygen base unit, active hydrogen content be 0.085% and viscosity be that 95 square millimeters/second linear siloxanes is dissolved in 65 and restrains in the tetrahydrofuran (THF)s, and sneak into 0.125 gram palladium/gac (Pd/C, the palladium of 10 weight %) and 28 milligrams of formic acid.Be heated to 70 ℃, and under this temperature, stirred 3 hours, and discharge hydrogen.In the perfect vacuum, under 80 ℃, remove all volatile components subsequently by distillment, and by the filtering separation catalyzer.Making viscosity and be 126 square millimeters/second and silanol group content is the product of the achromaticity and clarification of 84.7 mmoles/100 grams.The NMR spectrum analysis is the result show, quantitatively formed the chain side silanol group that is binding on the siloxane main chain.
Claims (13)
1, makes the method for the silicoorganic compound have silanol group and to form by following general formula unit
H
a′(R′O)
b(OH)
cR
dSiO
(4-a′-b-c-d)/2 (I)，
Wherein
A ' equals 0 or 1,
B equals 0 or 1,
C equals 0 or 1,
D equals 0,1,2 or 3,
R can be identical or different, and representative has the univalence hydrocarbyl that is substituted 1 to 18 carbon atom, silicon-carbon bond, optional, and
R ' can be identical or different, and representative can be by the heteroatoms optional univalence hydrocarbyl that is substituted at interval, and its condition is: a '+b+c+d's and≤3, a ' and c are not 1 simultaneously, and each molecule of silicoorganic compound of general formula (I) has at least one silicon bond OH base,
This method is by under the situation about existing at the catalyzer (B) that is selected from periodic table of elements VIII subgroup metal and compound thereof and optional cocatalyst (K), makes to have the SiH base and reacted with water (C) by the silicoorganic compound (A) that following general formula unit is formed
H
a(R′O)
bR
dSiO
(4-a-b-d)/2 (II)，
Wherein
A equals 0 or 1,
The definition of b, d, R and R ' is same as described above,
Its condition is: a+b+d and≤3,
And a '+c's and equal a,
And each molecule of silicoorganic compound of general formula (II) has at least one silicon bond hydrogen atom.
2, method according to claim 1 is characterized in that, a ' and b are equal to 0.
3, method according to claim 1 and 2 is characterized in that, as the silicoorganic compound with SiH base (A), uses to have following general formula person
Wherein
The integer that e equals 0 to 1000,
The integer that f equals 1 to 200,
R
1Represent hydrogen atom or R, and
R has the definition described in the claim 1.
4, according to the described method of one of claim 1 to 3, it is characterized in that, make the silicoorganic compound that comprise following general formula unit with silanol group,
Wherein
R has the definition described in the claim 1,
R
2Represent R or OH base,
G equals 0 to 199,
H equals 1 to 200,
Its condition is: g+h's and equal f, and
E and f have the definition described in the claim 3.
5, method according to claim 4 is characterized in that, g equals 0.
6, according to the described method of one of claim 1 to 5, it is characterized in that, use the catalyzer (B) that is incorporated on the solid support material.
7, according to the described method of one of claim 1 to 6, it is characterized in that, use the catalyzer (B) that is selected from following group: palladium, platinum, rhodium, ruthenium, iridium and compound thereof.
8, according to claim 6 or 7 described methods, it is characterized in that, use the solid support material that is selected from following group: SiO
2, Al
2O
3, clay, gac and organic resin.
9, according to the described method of one of claim 1 to 8, it is characterized in that, use the palladium that is incorporated on the gac as catalyzer (B).
10, according to the described method of one of claim 1 to 9, it is characterized in that, use the cocatalyst (K) that is selected from following group: organic acid and low-molecular-weight organosilicon hydride.
11, according to the described method of one of claim 1 to 10, it is characterized in that, use the cocatalyst (K) that is selected from following group: formic acid, acetic acid, oxalic acid, citric acid, xitix, triethyl silicane and tetramethyl disiloxane.
12, the silicoorganic compound that have silanol group, it has following general formula
Wherein
R has the definition described in the claim 1,
R
2Represent R or OH base,
G equals 0 to 199,
H equals 1 to 200,
Its condition is: g+h's and equal f, and
E and f have the definition described in the claim 3.
13, the silicoorganic compound with silanol group according to claim 12 is characterized in that g equals 0.
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| CN105492407A (en) * | 2013-08-28 | 2016-04-13 | 瓦克化学股份公司 | Curable organopolysiloxane compositions |
| CN111790377A (en) * | 2019-12-26 | 2020-10-20 | 东北石油大学 | Monoatomic catalyst, preparation method and application thereof |
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| DE102005018629A1 (en) * | 2005-04-21 | 2006-10-26 | Wacker Chemie Ag | Process for the preparation of triorganosiloxy-containing organopolysiloxanes |
| DE102006031107A1 (en) * | 2006-07-05 | 2008-01-10 | Wacker Chemie Ag | Hardenable Organopolysiloxanmassen |
| DE102007037292A1 (en) * | 2007-08-07 | 2009-02-12 | Evonik Goldschmidt Gmbh | Process for the preparation of branched polyorganosiloxanes |
| US8101242B2 (en) * | 2008-03-07 | 2012-01-24 | Sri International | Method of imparting corrosion resistance to a substrate surface, and coated substrates prepared thereby |
| CN107857882B (en) * | 2017-10-23 | 2021-08-03 | 杭州师范大学 | Fluorosilicone oil and preparation method thereof |
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| BE630246A (en) * | 1962-03-29 | |||
| US3504006A (en) * | 1964-07-29 | 1970-03-31 | Gen Electric | Process for preparing 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrocyclotetrasiloxane |
| GB2065661B (en) * | 1979-12-17 | 1984-02-15 | Gen Electric | Silicone foam compositions with burn resistant properties |
| KR910004647B1 (en) * | 1987-10-31 | 1991-07-09 | 고려화학 주식회사 | Stress reducing agents for encapsulating semiconductor |
| JPH0832829B2 (en) * | 1987-11-18 | 1996-03-29 | 東芝シリコーン株式会社 | Curable polyorganosiloxane composition |
| DE3742069A1 (en) * | 1987-12-11 | 1989-06-22 | Wacker Chemie Gmbh | METHOD FOR PRODUCING DIORGANOPOLYSILOXANS WITH TRIORGANOSILOXY GROUPS AS FINAL UNITS |
| JP3221893B2 (en) * | 1991-10-31 | 2001-10-22 | ダウ・コ−ニング・コ−ポレ−ション | Branched polyorganopolysiloxane |
| US5750643A (en) * | 1993-05-18 | 1998-05-12 | Sri International | Dehydrocoupling treatment and hydrosilylation of silicon-containing polymers, and compounds and articles produced thereby |
| US5346723A (en) * | 1993-07-12 | 1994-09-13 | Dow Corning Corporation | Method for curing organosiloxane compositions in the presence of cure inhibiting materials |
| JPH09104749A (en) | 1995-10-11 | 1997-04-22 | Shin Etsu Chem Co Ltd | Production of silanol-terminated polyoxyalkylene polymer |
| US5900438A (en) | 1997-08-08 | 1999-05-04 | Shin-Etsu Chemical Co., Ltd. | Thermosetting foamable organopolysiloxane composition and process of curing the same |
| JP3506358B2 (en) * | 1997-11-28 | 2004-03-15 | 信越化学工業株式会社 | Method for producing branched silicone oil |
| US6284906B1 (en) * | 1999-10-12 | 2001-09-04 | University Of Southern California | Cyclotrisiloxanes, new siloxane polymers and their preparation |
| JP3976113B2 (en) | 1999-11-26 | 2007-09-12 | 信越化学工業株式会社 | Method for producing branched silicone oil for condensation and equilibration at room temperature |
| JP4535603B2 (en) | 2000-11-17 | 2010-09-01 | 信越化学工業株式会社 | Cosmetics containing branched polysiloxane |
| JP3812647B2 (en) | 2001-09-07 | 2006-08-23 | 信越化学工業株式会社 | Method for producing siloxane having organooxy group or hydroxyl group |
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2005
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- 2006-03-30 DE DE502006000023T patent/DE502006000023D1/en active Active
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- 2006-04-12 US US11/402,613 patent/US7459514B2/en active Active
- 2006-04-19 JP JP2006115727A patent/JP4253664B2/en active Active
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105492407A (en) * | 2013-08-28 | 2016-04-13 | 瓦克化学股份公司 | Curable organopolysiloxane compositions |
| CN111790377A (en) * | 2019-12-26 | 2020-10-20 | 东北石油大学 | Monoatomic catalyst, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| EP1714995B1 (en) | 2007-06-27 |
| KR20060110841A (en) | 2006-10-25 |
| DE102005018628A1 (en) | 2006-10-26 |
| CN100436458C (en) | 2008-11-26 |
| US20060241268A1 (en) | 2006-10-26 |
| JP2006299265A (en) | 2006-11-02 |
| JP4253664B2 (en) | 2009-04-15 |
| DE502006000023D1 (en) | 2007-08-09 |
| KR100782094B1 (en) | 2007-12-04 |
| EP1714995A1 (en) | 2006-10-25 |
| US7459514B2 (en) | 2008-12-02 |
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